Method of producing an article comprising a rubber-like film-based article firmly fixed to a substrate

ABSTRACT

The present invention relates to a method including a rubber-like film-based article of which at least a portion is firmly fixed to a substrate. The method includes providing a film-based article made of a non-crosslinked thermoplastic rubber, contacting at least a portion of the film-based article with a substrate so as to form a contact area between the film-based article and the substrate, and heat sealing at least a portion of the contact area at a temperature of 190 to 250° C. for at least 1 second.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to European Patent Application No.20187815.4 filed on Jul. 27, 2020. The aforementioned application isincorporated herein by reference in its entirety.

TECHNICAL FIELD

The present invention relates to a method of producing an articlecomprising a rubber-like film-based article of which at least a portionis firmly fixed to a substrate.

BACKGROUND

Rubber-like film-based articles have to be firmly fixed to a substratein a plurality of applications. In some applications, the substrate isalso made of a rubber or rubber-like material and even of the samerubber or rubber-like material as the rubber-like film-based article.Thus, in these applications two or more rubber films may be adheredwhich each other to form a multilayer structure. Alternatively,different components of an article are adhered to each other to form thefinal article having a complex design, wherein some or all of thecomponents are made of a rubber or rubber-like material. In otherapplications, the substrate is made of a non-rubber material, such as ofpolyurethane, polyethylene terephthalate, nylon, polyethylene or thelike. For example, certain balloon catheters comprise a balloon asfilm-based article made of rubber or rubber-like material, wherein theballoon is fixed to a tube as substrate made for instance ofpolyurethane. In other applications a surgical glove as film-basedarticle made of rubber is adhered to a sleeve as substrate made ofpolyethylene or to a fabric substrate, such as the arm component of asurgical coat. Other examples are rubbery breathable films for wounddressing, rubber-like seals for protective suits, shoes with rubbersoles, clothes with rubber parts and the like.

Usually, rubber film-based articles, i.e. articles made of one or morefilms made of vulcanized or crosslinked rubber, respectively, are fixedto a substrate made of rubber, of a rubber-like material, of anon-rubber polymeric material or of a fabric, by means of a glue oradhesive, respectively. However, this is connected with severaldisadvantages. Firstly, the seal strength of glue bonds is in aplurality of cases not sufficient or the seal strength is initiallyacceptable, but reduces over the time to an inacceptable value, thuslimiting the service life of these articles. Moreover, glues are mostlynot heat-resistant, but softens with increasing temperature, which alsolimits the service life of these articles. In addition, the peelstrength as well as impact resistance of a glue bond is typically quitelow. Furthermore, reproducible fixing two complex shaped components toeach other with a glue is a challenge.

SUMMARY

In view of the above, the object underlying the present invention is toprovide a method of producing an article comprising a rubber-likefilm-based article of which at least a portion is firmly fixed to asubstrate, which does not need the use of a glue, adhesive or the like,but which nevertheless leads to an article, in which the rubber-likefilm-based article is firmly and permanently fixed to a substrate.

In accordance with the present invention, this object is satisfied byproviding a method of producing an article comprising a rubber-likefilm-based article of which at least a portion is firmly fixed to asubstrate, comprising the following steps:

-   -   a) providing a film-based article made of a non-crosslinked        thermoplastic rubber,    -   b) contacting at least a portion of the film-based article with        a substrate so as to form a contact area between the film-based        article and the substrate and    -   c) heat sealing at least a portion of the contact area at a        temperature of 190 to 250° C. for at least 1 second.

By using a non-crosslinked thermoplastic rubber film-based article, thefilm-based article may be heat sealed with the substrate, which is notpossible, if a vulcanized, i.e. crosslinked, rubber is used. Heatsealing leads to a firm and in particular permanently firm bond betweenthe substrate and the film-based article. In particular, when thenon-crosslinked thermoplastic rubber film-based article is heat sealedwith a substrate made of the same or a different non-crosslinkedthermoplastic rubber, excellently high seal strengths are obtained.Therefore, the use of a glue is not at all necessary and theaforementioned disadvantages connected with the use of a glue areavoided in the method in accordance with the present invention. However,if appropriately selecting the non-crosslinked thermoplastic rubbermaterial, a film-based articles with rubber-like mechanical propertiesrequired for the application, such as an appropriate tensile strength,appropriate elasticity, appropriate modulus, appropriate punctureresistance and the like, i.e. being concerning the properties equivalentto vulcanized rubber film-based articles may be produced and used in thearticle.

DETAILED DESCRIPTION

The term “non-crosslinked thermoplastic rubber” means in accordance withthe present invention any thermoplastic elastomer, i.e. any copolymerhaving thermoplastic as well as elastomeric properties.

“Copolymer” means in accordance with the present invention any polymercomprising more than one monomer, i.e. biopolymers, terpolymers, quarterpolymers and more monomers comprising polymers.

“Film-based article” denotes in accordance with the present inventionany article, which is made of one or more films having a thickness of atmost 20 mm, such as gloves, catheter balloons, shoe soles or the like.Thus, the term “film-based article” also covers a film or, in otherwords, a film is considered in the present patent application to be afilm-based article.

In step a) a film-based article made of a non-crosslinked thermoplasticrubber is provided. The film-based article made of a non-crosslinkedthermoplastic rubber is an article comprising at least 50% by weight,preferably at least 75% by weight, more preferably at least 90% byweight, even more preferably at least 95% by weight and still morepreferably at least 98% by weight. Most preferably, the film-basedarticle made of a non-crosslinked thermoplastic rubber completelyconsists of a respective rubber.

Preferably, the non-crosslinked thermoplastic rubber used in step a) ofthe method in accordance with the present invention is a thermoplasticstyrenic block copolymer. Thermoplastic styrenic block copolymers allowto produce film-based articles with suitable rubber-like mechanicalproperties, such as an appropriate tensile strength, elasticity, modulusand puncture resistance.

Examples for suitable thermoplastic styrenic block copolymers are thosebeing selected from the group consisting of styrene-isoprene-styreneblock copolymers (SIS), styrene-isobutylene-styrene block copolymers(SIBS), styrene-butadiene-styrene block copolymers (SBS),styrene-ethylene-butylene-styrene block copolymers (SEBS),styrene-ethylene-propylene-styrene block copolymers (SEPS),styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS) andarbitrary combinations of two or more of the aforementionedthermoplastic styrenic block copolymers.

Good results are in particular obtained, when the thermoplastic styrenicblock copolymer is a styrene-isoprene-styrene block copolymer (SIS).

In accordance with a particular preferred embodiment of the presentinvention, the non-crosslinked thermoplastic rubber used in step a) ofthe method in accordance with the present invention is a branched blockcopolymer of the general formula (I):

A-B—Y—(B-A)_(n)  (I),

wherein

each A is independently a polymer block composed of at least 80 mol. %of an alkenyl aromatic hydrocarbon,

the content of A by weight of the total weight of the polymer is in therange of 5 to 20%,

Y is the remnant of a coupling agent having a functionality greater than2,

the degree of branching is n+1, wherein n is an integer from 2 to 4,

each B is independently an olefinically unsaturated polymer blockcomposed of at least 80 mol. % of one or more conjugated dienes and

the block copolymer has a coupling efficiency in the range of 70 to100%.

Films made of this material do not only have suitable mechanicalproperties, such as an excellent tensile strength and elasticity, butare also heat sealable leading to a heat sealed article having a veryhigh sealing strength.

Good results are in particular obtained, when each A block independentlyhas a weight average molecular weight ranging from 10,000 to 12,000g/mol and/or each B Block independently has a weight average molecularweight ranging from 80,000 to 120,000 g/mol. In accordance with thepresent invention the molecular weights are determined pursuant to ASTM3536 using mono-dispersed polystyrene standards.

In a further development of the idea of the present invention it isproposed that the non-crosslinked thermoplastic rubber used in step a)is a branched block copolymer of the general formula (I), wherein

each A is independently a polymer block composed of at least 90 mol. %of an alkenyl aromatic hydrocarbon,

the content of A by weight of the total weight of the polymer is in therange of 9 to 12%,

each B is independently an olefinically unsaturated polymer blockcomposed of at least 90 mol. % of one or more conjugated dienes and

the block copolymer has a coupling efficiency in the range of 84 to100%.

Even more preferably, the degree of branching is 4 and the couplingefficiency is 90 to 100%.

In a further development of the idea of the present invention, thenon-crosslinked thermoplastic rubber used in step a) of the method inaccordance with the present invention is a branched block copolymer ofthe general formula (I), in which each B is a polymer block composed ofat least 90 mol. % of isoprene and each A is a polymer block composed ofat least 90 mol. % of styrene. In this embodiment, the non-crosslinkedthermoplastic rubber used in step a) is a branched SIS.

Thus, most preferably the non-crosslinked thermoplastic rubber used instep a) of the method in accordance with the present invention is abranched block copolymer of the general formula (I), wherein

each A is independently a polymer block composed of at least 90 mol. %of styrene,

the content of A by weight of the total weight of the polymer is in therange of 9 to 12%,

Y is the remnant of a coupling agent having a functionality greater than2,

the degree of branching is n+1, wherein n is an integer from 2 to 4,

each B is independently an olefinically unsaturated polymer blockcomposed of at least 90 mol. % of isoprene,

the block copolymer has a coupling efficiency in the range of 84 to100%,

each A block independently has a weight average molecular weight rangingfrom 10,000 to 12,000 g/mol and

each B Block independently has a weight average molecular weight rangingfrom 80,000 to 120,000 g/mol.

The present invention is not particularly limited concerning thethickness of the film, from which the film-based article provided instep a) is made, as long as the film has sufficiently good mechanicalproperties and the film is not too thick that a heat sealing cannot bepracticed anymore. For example, the film of the film-based articleprovided in step a) may have a thickness of 1 μm to 10 mm, preferably of10 μm to 1 mm, more preferably of 50 μm to 500 μm and most preferably of150 μm to 250 μm.

Concerning the method for preparing the film-based article provided instep a), the present invention is not particularly limited. An examplefor an easy and cost-efficient method for producing the film-basedarticle provided in step a), which even allows to prepare film-basedarticles with a complex form with a minimum dimensional tolerance, iscoagulation dipping using a latex of the non-crosslinked thermoplasticrubber. Coagulation dipping bases on the formation of a polymer film bydipping a mold with a surface profile complying to that of the film tobe formed first into a coagulation agent, so as to bind coagulationagent onto the surface of the mold, before the so treated mold is dippedinto rubber latex. On account of the coagulation agent on the surface ofthe mold, the rubber contained in the latex coagulates and precipitateson the surface of the mold leading to a film-based article in the formof the surface profile of the mold. As set out above, in the presentinvention specifically latex of non-crosslinked thermoplastic rubber isused so that the term “latex” means a dispersion of the particles ofnon-crosslinked thermoplastic rubber in a medium, preferably in anaqueous medium.

More specifically, the coagulation dipping may comprise the followingsteps:

-   -   i) dipping a mold into a coagulant solution,    -   ii) removing the mold from the coagulant solution and drying the        mold,    -   iii) dipping the dried mold into a latex of the non-crosslinked        thermoplastic rubber so as to form a film-based article made of        a non-crosslinked thermoplastic rubber on the mold,    -   iv) removing the mold with the film-based article thereon from        the latex and pre-curing the film,    -   v) optionally leaching the film-based article in water,    -   vi) curing the film-based article and    -   vii) removing the film-based article from the mold.

Usually, the mold will be cleaned and dried in an oven e.g. at about100° C., before it is used in step i).

Preferably, the coagulant solution is an aqueous solution containing oneor more different alkaline earth metal salts. Good results are inparticular obtained with aqueous solutions containing a calcium salt,which has a sufficiently high solubility in water, such as calciumchloride or calcium nitrate. The content of the alkaline earth metalsalt(s) in the aqueous solution may be between 5 and 40% by weight, suchas 10 to 20% by weight, such as about 15% by weight. A dipping time of15 to 60 seconds and preferably 25 to 40 seconds is usually enough tobind a sufficient amount of the coagulation agent onto the surface ofthe mold.

The mold removed in step ii) from the coagulant solution may be dried inan oven at a temperature between 90 to 110° C., before it is dipped instep iii) into a latex of the non-crosslinked thermoplastic rubber so asto form a film-based article made of a non-crosslinked thermoplasticrubber on the mold. The latex is preferably an aqueous dispersion of thenon-crosslinked thermoplastic rubber in water, wherein the latex haspreferably a concentration of the non-crosslinked thermoplastic rubberof 50 to 80% by weight, more preferably of 60 to 70% by weight and mostpreferably of 63 to 67% by weight. In order to obtain a particularhomogeneous distribution of the non-crosslinked thermoplastic rubberparticles in the latex, it is suggested that the latex contains smallamounts of a surfactant, preferably of an anionic surfactant, such as arosin acid salt. The latex used step iii) may be a latex being dilutedto a concentration of the non-crosslinked thermoplastic rubber of 30 to35% by weight.

The latex may be prepared by a method comprising the following steps:

-   -   a) emulsifying a solution of the non-crosslinked thermoplastic        rubber with soap in a high shear mixer,    -   b) removing the solvent of the so formed emulsion,    -   c) adjusting the solid content of the so obtained solvent free        emulsion and    -   d) pasteurizing the so obtained latex.

The mold with the film-based article thereon as removed from the latexis precured in step iv) preferably at a temperature between 90 to 110°C. for 30 to 60 seconds and preferably at a temperature between 95 to105° C. for 50 to 70 seconds, such as about 30 or about 60 seconds.

After having removed the film-based article in step v) from the mold,after the optional leaching of the film-based article in water,preferably in hot water (such as in water having a temperature of 40 to60° C. for 1 to 10 minutes, such as in water having a temperature ofabout 50° C. for about 5 minutes), in step vi) so as to remove remainingchemicals, such as surfactant, from the film-based article, thefilm-based article is finally cured in step vii). Good results are inparticular obtained, when the curing is performed for 10 to 30 minutesat 80 to 150° C. and more preferably for 15 to 25 minutes at 100 to 120°C.

Concerning the substrate, the present invention is not particularlylimited, as long as the substrate is able to be heat sealed with thefilm-based article. For example, the substrate may be made of a materialbeing selected from the group consisting non-crosslinked thermoplasticrubbers, polyamides, polyesters, thermoplastic polyurethanes andarbitrary combinations of two or more of the aforementioned materials.

Best results in view of the obtained seal strength are achieved, whenthe substrate is made—as the film-based article, to which it is fixed byheat sealing—from a non-crosslinked thermoplastic rubber and mostpreferably from the same non-crosslinked thermoplastic rubber as thefilm-based article. In particular, the substrate may a film-basedarticle and even the same film-based article, so that in this embodimenttwo same film-based articles may be fixed with each other by means ofheat sealing. In that case seal strengths of more than 20 N/25 mm may beobtained. In this embodiment, articles with a multilayer structure maybe produced by heat sealing two or more films or formed film-basedarticles made of the same or at least very similar material onto eachother. Alternatively, this embodiment may be used to produce verycomplex formed articles by heat sealing components of the finalstructure to each other.

The substrate may be in another embodiment a fabric, such as a fabricmade of wool or of a thermoplastic polymer. The porous surface structureof such a fabric supports the heat sealing.

In accordance with the present invention, the heat sealing is performedin step c) at a temperature of 190 to 250° C. for at least 1 second.Preferably, the heat sealing is performed in this temperature range forat least 5 seconds, more preferably for at least 10 seconds, still morepreferably for at least 20 seconds, even more preferably for at least 30seconds and most more preferably for at least 50 seconds, such as forabout 60 seconds. The upper limit for the heat sealing time is notparticularly limited and may be 240 seconds, 180 seconds or 120 seconds.

In accordance with a particular preferred embodiment of the presentinvention, in particular when using a film-based article made of a blockcopolymer of the general formula (I), the heat sealing is performed instep c) at a temperature of 190 to 230° C., more preferably at atemperature of 190 to 220° C., even more preferably at a temperature of195 to 210° C., such as at about 200° C.

Moreover, it is preferred that the heat sealing is performed in step c)at ambient pressure or under slight over-ambient pressure.

The heat sealing may be performed with any commercially available heatsealing devise, such as those using a heat sealing bar. This allows thatthat the pressure and temperature during the heat sealing is the same orat least essentially the same over the heat sealed contact area.

In most applications, the heat sealing with be performed in step c)along a line on the contact area formed in step b) between thefilm-based article and the substrate. However, it is also possible toheat seal the film-based article with the substrate along two or morelines, which may be all in the border area of the film-based articleand/or substrate. Typically, the width of the heat sealed portion willbe 3 to 5 mm.

As set out above, depending on the materials of the film of thefilm-based article and of the substrate, very high seal strength may beobtained. Thus, preferably the seal strength of the heat sealed contactarea between the film-based article and the substrate is at least 5 N/25mm, more preferably at least 5 N/25 mm, even more preferably at least 6N/25 mm, still more preferably at least 7 N/25 mm, yet more preferablyat least 9 N/25 mm, yet more preferably at least 12 N/25 mm, yet morepreferably at least 15 N/25 mm and most preferably at least 20 N/25 mm.In accordance with the present invention, the seal strength is measuresas defined in ASTM F88-F88M. For instance, the seal strength may bedetermining by using an Instron 3365 tensile machine. Each tail of thespecimen of the film-based article is secured in the opposing grips ofthe tensile machine and the seal remains unsupported during testing.Then a rate of grip separation of 500 mm/min may be used, wherein theforce is measured by a load-cell on top of the Instron 3365 tensilemachine and the results are reported in Newton/25 mm.

Due to the high seal strength obtainable with the method in accordancewith the present invention, the method does not require the use of aglue or of an adhesive coating. Therefore, preferably the method inaccordance with the present invention is performed without using a glueand without using an adhesive coating.

Moreover, it is preferred that the method in accordance with the presentinvention does not comprise any corona discharge treatment.

A further aspect of the present invention is an article comprising arubber-like film-based article of which at least a portion is firmlyfixed to a substrate, which is obtainable with the aforementionedmethod.

In a further development of the idea of the present invention it ispreferred that the film-based article has at least one of the followingproperties, namely i) a tensile strength of at least 19 MPa, ii) a 10%Young's modulus of less than 0.25 MPa and iii) a complex modulus at 120°C. of at least 5.6×10⁵ Pa·s, and that the seal strength of the heatsealed contact area between the film-based article and the substrate isat least 5 N/25 mm, preferably at least 5 N/25 mm, more preferably atleast 6 N/25 mm, even more preferably at least 7 N/25 mm, still morepreferably at least 9 N/25 mm, yet more preferably at least 12 N/25 mm,yet more preferably at least 15 N/25 mm and most preferably at least 20N/25 mm. More preferably, the film-based article provided in step a) hasat least two of the aforementioned properties i), ii) and iii) and mostpreferably the film-based article provided in step a) has all threeproperties i), ii) and iii). The tensile strength is preferably measuredaccording to ASTM D412. The Young's modulus in Pa is calculated by theequation E=tensile stress/tensile strain=(F*L)/(A*ΔL), wherein F is theapplied force, L is the initial length, A is the cross-sectional areaand ΔL is the change in length. The tensile properties mentioned in thisequation are measured according to ASTM D412. The complex modulusdetermined in accordance with ISO 6721-4:2019.

The article according to the present invention may comprise asrubber-like film-based article a surgical glove and as substrate asurgical coat or the arm portion of a surgical coat, wherein the contactarea between the surgical glove and the surgical coat is preferably inthe terminal end portion being opposite to the finger portion of theglove and at an appropriate position of the surgical coat so that itfits to a person wearing it.

In an alternative embodiment of the present invention, the articlecomprises as film-based article as well as as substrate are rubber-likefilm-based articles, wherein the substrate and the film-based articleindependently from each other are selected from the group consisting ofgloves, customized clothes, articles of the pleasure industry, shoesoles and arbitrary combinations of two or more of the aforementionedforms.

In still an alternative embodiment of the present invention, the articlecomprises as rubber-like film-based article a catheter balloon and assubstrate a catheter tube made of a thermoplastic polymer and preferablyof thermoplastic polyurethane.

In yet an alternative embodiment of the present invention, the articlecomprises as substrate a breathable film for wound dressing, a sleevefor rubber gloves or a rubberlike seal for protective suits.

As set out above, according to the present invention it is possible andactually preferred that the film-based article and the substrate are notfixed to each other by means of a glue or an adhesive coating.

Subsequently, the present invention is illustrated by means ofnon-limiting examples.

Examples 1 to 3

Films made of a non-crosslinked thermoplastic rubber were prepared bycoagulation dipping using as latex Cariflex IR2GL1 distributed byCariflex Pte. Ltd. having been diluted to a solid content of 35% byweight, which is a latex of a block copolymer falling under the generalformula (I), comprising the following steps

-   -   A mold or former, respectively, was cleaned and dried at 100°        C.,    -   the former was dipped in a coagulant solution, namely an aqueous        solution comprising 15% by weight of calcium nitrate,    -   the former was removed from the solution and dried at 100° C.,    -   the former was dipped in the aforementioned latex,    -   the former with the latex film formed thereon was removed from        the latex and pre-cured for 1 minute at 100° C.,    -   the latex film on the former was leached in water having a        temperature of 50° C. for 5 minutes,    -   the film on the former was cured in an oven at 120° C. for 20        minutes,    -   the former with the film formed was cooled down to ambient        temperature and then the film was removed from the former.

The so obtained film of non-crosslinked thermoplastic rubber was thencut into strips of 25 mm width and had a thickness of 0.30 mm.

The aforementioned method was repeated so as to obtain films ofnon-crosslinked thermoplastic rubber with a width of 25 mm and with athickness of 0.22 mm and 0.43 mm, respectively.

In example 1, strips with a thickness of 0.22 mm were sealed together,in example 2 strips with a thickness of 0.30 mm and in example 3 stripswith a thickness of 0.43 mm. The strips were laid above each other andsealed together along a line of the contact area having a width of 2 to3 mm and a length of 25 mm with a Rajasystem, which was manuallyoperated, wherein hand pressure was applied to the heat sealer. Theoff-line measured temperature during sealing was 190 to 220° C.

Afterwards, the seal strength of the heat sealed contact area wasmeasured by using an Instron 3365 tensile machine. Each tail of thespecimen of the heat sealed film laminated was secured in the opposinggrips of the tensile machine and the seal remains unsupported duringtesting. Then a rate of grip separation of 500 mm/min was used, whereinthe force was measured by a load-cell on top of the Instron 3365 tensilemachine and the results were recorded in Newton/25 mm. Moreover, it wasnoted and recorded, where the break started, i.e. in one of the twofilms or in the seal area.

The following results were obtained:

TABLE 1 Results Film thickness Seal strength Example (mm) (N/25 mm)Break in 1 0.22 31 film 2 0.30 28 seal 3 0.43 10 film

Examples 4 to 11

Strips of a film of non-crosslinked thermoplastic rubber having a widthof 25 mm and a thickness of 0.30 mm as described for examples 1 to 3were heat sealed under conditions as described above for examples 1 to 3to substrates made of other materials. These were film strips made ofpolyurethane distributed by Huntsman as PU Irogran® with the productcodes 1778E4506 (example 4), A85E4993 (example 5), A85E4994 (example 6),A92E5670 (example 7), made of polyurethane distributed by Gerlingerindustries (example 8), made of nylon (example 9), made of polyester(example 10) and made of polyethylene (example 11).

The following results were obtained:

TABLE 2 Results Seal strength Example (N/25 mm) Break in 4 4.2 seal 54.5 seal 6 4.8 seal 7 4.3 seal 8 4.3 seal 9 6.3 seal 10 5.3 seal 11 6.2seal

COMPARATIVE EXAMPLE

Example 1 was repeated except that the strip of film formed of CariflexIR2GL1 was not heat sealed to another strip of the same film, but to astrip made of isoprene rubber latex Cariflex IR0401.

No heat seal could be achieved.

1. A method of producing an article comprising a rubber-like film-based article of which at least a portion is firmly fixed to a substrate, comprising: a) providing a film-based article made of a non-crosslinked thermoplastic rubber; b) contacting at least a portion of the film-based article with a substrate so as to form a contact area between the film-based article and the substrate; and c) heat sealing at least a portion of the contact area at a temperature of 190 to 250° C. for at least 1 second.
 2. The method according to claim 1, wherein the non-crosslinked thermoplastic rubber is a thermoplastic styrenic block copolymer, which is preferably selected from the group consisting of styrene-isoprene-styrene block copolymers (SIS), styrene-isobutylene-styrene block copolymers (SIBS), styrene-butadiene-styrene block copolymers (SBS), styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS) and arbitrary combinations of two or more of the aforementioned thermoplastic styrenic block copolymers.
 3. The method according to claim 1, wherein the non-crosslinked thermoplastic rubber is a block copolymer of the general formula (I): A-B—Y—(B-A)_(n)  (I), wherein each A is independently a polymer block composed of at least 90 mol. % of an alkenyl aromatic hydrocarbon, the content of A by weight of the total weight of the polymer is in the range of 9 to 12%, Y is the remnant of a coupling agent having a functionality greater than 2, the degree of branching is n+1, wherein n is an integer from 2 to 4, each B is independently an olefinically unsaturated polymer block composed of at least 90 mol. % of one or more conjugated dienes, the block copolymer has a coupling efficiency in the range of 84 to 100%, preferably each A block independently has a weight average molecular weight ranging from 10,000 to 12,000 g/mol, and preferably each B Block independently has a weight average molecular weight ranging from 80,000 to 120,000 g/mol, wherein the molecular weights are determined pursuant to ASTM 3536 using mono-dispersed polystyrene standards.
 4. The method according to claim 3, wherein in the formula (I) each B is a polymer block composed of at least 90 mol. % of isoprene and each A is a polymer block composed of at least 90 mol. % of styrene.
 5. The method according to claim 1, wherein the film of the film-based article provided in step a) has a thickness of 1 μm to 10 mm, preferably of 10 μm to 1 mm, more preferably of 50 μm to 500 μm and most preferably of 150 μm to 250 μm.
 6. The method according to claim 1, wherein the film-based article provided in step a) has been prepared by coagulation dipping using a latex of the non-crosslinked thermoplastic rubber, wherein the coagulation dipping preferably comprises: i) dipping a mold into a coagulant solution; ii) removing the mold from the coagulant solution and drying the mold; iii) dipping the dried mold into a latex of the non-crosslinked thermoplastic rubber so as to form a film-based article made of a non-crosslinked thermoplastic rubber on the mold; iv) removing the mold from the latex and pre-curing the latex with the film-based article; v) optionally leaching the film-based article in water; vi) curing the film-based article; and vii) removing the film-based article from the mold.
 7. The method according to claim 1, wherein the substrate is made of a material being selected from the group consisting of non-crosslinked thermoplastic rubbers, polyamides, polyesters, thermoplastic polyurethanes and arbitrary combinations of two or more of the aforementioned materials.
 8. The method according to claim 1, wherein the substrate is a fabric.
 9. The method according to claim 1, wherein the heat sealing is performed at a temperature of 190 to 250° C. for at least 10 seconds, preferably for at least 20 seconds, more preferably for at least 30 seconds and most more preferably for at least 50 seconds.
 10. The method according to claim 1, wherein the seal strength of the heat sealed contact area between the film-based article and the substrate is at least 5 N/25 mm, preferably at least 5 N/25 mm, more preferably at least 6 N/25 mm, even more preferably at least 7 N/25 mm, still more preferably at least 9 N/25 mm, yet more preferably at least 12 N/25 mm, yet more preferably at least 15 N/25 mm and most preferably at least 20 N/25 mm.
 11. The method according to claim 1, wherein neither a glue nor an adhesive coating is used, and wherein no corona discharge treatment is made.
 12. An article comprising a rubber-like film-based article of which at least a portion is firmly fixed to a substrate, which is obtainable with a method according to claim
 1. 13. The article according to claim 12, wherein the film of the film-based article has tensile strength of at least 19 MPa, a 10% Young's modulus of less than 0.25 MPa and a complex modulus at 120° C. of at least 5.6×10⁵ Pa·s, and wherein the seal strength of the heat sealed contact area between the film of the film-based article and the substrate is at least 5 N/25 mm, preferably at least 5 N/25 mm, more preferably at least 6 N/25 mm, even more preferably at least 7 N/25 mm, still more preferably at least 9 N/25 mm, yet more preferably at least 12 N/25 mm, yet more preferably at least 15 N/25 mm and most preferably at least 20 N/25 mm.
 14. The article according to claim 12, wherein i) the rubber-like film-based article has the form of a surgical glove and the substrate is a surgical coat or the arm portion of a surgical coat, or ii) the film-based article as well as the substrate are a rubber-like film-based article, wherein the substrate and the film-based article independently from each other is selected from the group consisting of gloves, customized clothes, articles of the pleasure industry, shoe soles and arbitrary combinations of two or more of the aforementioned forms, or iii) the rubber-like film-based article has the form of a catheter balloon and the substrate is a catheter tube made of a thermoplastic polymer and preferably of thermoplastic polyurethane, or iv) the substrate is a breathable film for wound dressing, a sleeve for rubber gloves or a rubberlike seal for protective suits.
 15. The article according to any of claim 12, wherein the film-based article and the substrate are not fixed to each other by means of a glue or an adhesive coating. 